Hydrochlorofluorocarbons having OH rate constants which do not contribute substantially to ozone depletion and global warming

ABSTRACT

The present invention provides hydrochlorofluorocarbons having 3 to 5 carbons atoms, 1 to 2 chlorine atoms, and an OH rate constant from about 8 to about 25 cm 3  /molecule/sec×10 -14 . The hydrochlorofluorocarbons are useful as solvents and blowing agents.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 08/232,979 filed on April 25, 1994 now abandoned which is a division of application Ser. No. 07/746,449 filed on Aug. 16, 1991 now U.S. Pat. No. 5,316,690.

BACKGROUND OF THE INVENTION

The present invention relates to a class of hydrochlorofluorocarbons which have 3 to 5 carbon atoms, have 1 to 2 chlorine atoms, and have OH rate constants from about 8 to about 25 cm³ /molecule/sec×10⁻¹⁴.

Vapor degreasing and solvent cleaning with fluorocarbon based solvents have found widespread use in industry for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.

In its simplest form, vapor degreasing or solvent cleaning consists of exposing a room-temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.

For soils which are difficult to remove, where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the cleaning of metal parts and assemblies must be done efficiently and quickly, the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part. In addition, the part can also be sprayed with distilled solvent before final rinsing.

Vapor degreasers suitable in the above-described operations are well known in the art. For example, Sherliker et al. in U.S. Pat. No. 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean slump, a water separator, and other ancilliary equipment.

Cold cleaning is another application where a number of solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with rags or similar objects soaked in solvents.

In cold cleaning applications, the use of the aerosol packaging concept has long been found to be a convenient and cost effective means of dispensing solvents. Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquified gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve. The propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems.

Chlorofluorocarbon solvents, such as trichlorotrifluoroethane, have attained widespread use in recent years as effective, nontoxic, and nonflammable agents useful in degreasing applications and other solvent cleaning applications. Trichlorotrifluoroethane has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts and the like. Trichlorotrifluoroethane has two isomers: 1,1,2-trichloro-1,2,2-trifluoroethane (known in the art as CFC-113) and 1,1,1-trichloro-2,2,2-trifluoroethane (known in the art as CFC-113a). CFC-113 has a boiling point of about 47° C. and has been found to have satisfactory solvent power for greases, oils, waxes, and the like.

Another commonly used solvent is chloroform (known in the art as HCC-20) which has a boiling point of about 63° C. Perchloroethylene is a commonly used dry cleaning and vapor degreasing solvent which has a boiling point of about 121° C. These compounds are disadvantageous for use as solvents because they are toxic; also, chloroform causes liver damage when inhaled in excess.

Although chlorine is known to contribute to the solvency capability of a compound, fully halogenated chlorofluorocarbons and hydrochlorofluorocarbons are suspected of causing environmental problems in connection with the earth's protective ozone layer. Thus, the art is seeking new compounds which do not contribute to environmental problems but yet provide the solvency properties of CFC-113.

Chlorofluorocarbons (CFCs) such as CFC-113 are suspected of causing environmental problems in connection with the ozone layer. Under the Clean Air Act, CFC-113 is being phased-out of production.

In response to the need for stratospherically safe materials, substitutes have been developed and continue to be developed. Research Disclosure 14623 (June 1978) reports that 1,1-dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) is a useful solvent for degreasing and defluxing substrates. In the EPA "Findings of the Chlorofluorocarbon Chemical Substitutes International Committee", EPA-600/9-88-009 (April 1988), it was reported that HCFC-123 and 1,1-dichloro-1-fluoroethane (known in the art as HCFC-141b) have potential as replacements for CFC-113 as cleaning agents.

The problem with these substitutes is that they have a long atmospheric lifetime as determined by their reaction with OH radicals in the troposphere. Table I below contains the OH rate constants and corresponding atmospheric lifetimes for these Substitutes. In Table I, Exp KOH stands for experimental KOH rate constant, Est KOH stands for estimated KOH rate constant, Exp Life stands for experimental lifetime, and Est Life stands for estimated lifetime. The unit on the rate constant is cm³ /molecule/sec×10⁻¹⁴ and the unit on the lifetime is years.

                  TABLE I                                                          ______________________________________                                                               Exp    Est   Exp  Est                                    Number   Formula      KOH    KOH   Life Life                                   ______________________________________                                         HCFC-123 CHC12CF3     3.7    2.96  2.0  2.6                                    HCFC-124 CF3CHClF     1.0    1.00  7.5  7.5                                    HCFC-141b                                                                               CFCl2CH3     0.75   2.10  10.1 3.6                                    HCFC-142b                                                                               CF2ClCH3     0.38   2.10  19.9 6                                      HCFC-225ca                                                                              CF3CF2CHCF2  2.49   3.30  2.3  2.3                                    HCFC-225cb                                                                              CClF2CF2CHClF                                                                               0.91   3.86  2     1.96                                  HCC-140  CCl3CH3      1.2    1.21  6.3  6.3                                    ______________________________________                                    

It would be desirable to have substitutes with OH rate constants of at least about 8 cm³ /molecule/sec×10⁻¹⁴ which equates to an atmospheric lifetime of 12 months or less.

If the OH rate constant of a compound is too high, the compound is a VOC (Volatile Organic Compound) because it is so reactive that it forms carbon dioxide which contributes to global warming. Thus, it would be desirable to have substitutes with OH rate constants of 25 cm³ /molecule/sec×10⁻¹⁴ or less which equates to an atmospheric lifetime of at least 4 months.

Commonly assigned U.S. Pat. No. 4,947,881 teaches a method of cleaning using hydrochlorofluoropropanes having 2 chlorine atoms and a difluoromethylene group. European Publication 347,924 published Dec. 27, 1989 teaches hydrochlorofluoropropanes having a difluoromethylene group. International Publication Number WO 90/08814 published Aug. 9, 1990 teaches azeotropes having at least one hydrochlorofluoropropane having a difluoromethylene group.

A wide variety of consumer parts is produced on an annual basis in the United States and abroad. Many of these parts have to be cleaned during various manufacturing stages in order to remove undesirable contaminants. These parts are produced in large quantities and as a result, substantial quantities of solvents are used to clean them.

Thus, substitutes having OH rate constants between about 8 and about 25 cm³ /molecule/sec×10⁻¹⁴ and which are useful in many applications including as solvents are needed in the art.

SUMMARY OF THE INVENTION

Straight chain and branched chain hydrochlorofluorocarbons having 3 to 5 carbon atoms and 1 or 2 chlorine atoms total over 1100 compounds. Out of this over 1100 compounds, I was surprised to find a class of 88 hydrochlorofluorocarbons having OH rate constants from about 8 to about 25 cm³ /molecule/sec×10⁻¹⁴.

The OH rate constant can be determined by any method known in the art. For example, see Atkinson, "Kinetics and Mechanisms of the Gas-Phase Reactions of the Hydroxyl Radical with Organic Compounds under Atmospheric Conditions", Chem. Rev, 86, 69 (1986) and Taylor et al., "Laser Photolysis/Laser-Induced Fluorescence Studies of Reaction Rates of OH with CH₃ Cl, CH₂ Cl₂, and CHCl3 over an Extended Temperature Range", Int. J. of Chem, Kinetics 21, 829 (1989).

The straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention are listed in Table II below. The unit on the calculated KOH is cm³ /molecule/sec×10⁻¹⁴ and the unit on the calculated lifetime is years in Table II.

                  TABLE II                                                         ______________________________________                                         Number     Chemical Formula                                                                             KOH    Lifetime                                       ______________________________________                                         HCFC-234aa CF.sub.2 HCCl.sub.2 CF.sub.2 H                                                               24.5   0.30                                           HCFC-234ab CFH.sub.2 CCl.sub.2 CF.sub.3                                                                 11.9   0.64                                           HCFC-234ba CF.sub.2 HCFClCFClH                                                                          22.9   0.33                                           HCFC-234bb CF.sub.3 CFClCClH.sub.2                                                                      9.5    0.80                                           HCFC-234bc CFH.sub.2 CFClCF.sub.2 Cl                                                                    13.1   0.58                                           HCFC-234fa CF.sub.2 ClCH.sub.2 CF.sub.2 Cl                                                              8.2    0.92                                           HCFC-234fb CF.sub.3 CH.sub.2 CFCl.sub.2                                                                 8.2    0.92                                           HCFC-243ea CFClHCFHCFClH 19.1   0.40                                           HCFC-243ec CF.sub.2 ClCFHCClH.sub.2                                                                     8.4    0.90                                           HCFC-244ba CFH.sub.2 CFClCF.sub.2 H                                                                     12.0   0.63                                           HCFC-244da CF.sub.2 HCClHCF.sub.2 H                                                                     11.85  0.64                                           HCFC-244db CF.sub.3 CClHCFH.sub.2                                                                       9.3    0.81                                           HCFC-244ea CF.sub.2 HCFHCFClH                                                                           11.9   0.64                                           HCFC-244eb CF.sub.3 CFHCClH.sub.2                                                                       10.5   0.72                                           HCFC-244ec CFH.sub.2 CFHCF.sub.2 Cl                                                                     10.1   0.75                                           HCFC-244fa CFClHCH.sub.2 CF.sub.3                                                                       8.5    0.89                                           HCFC-244fb CF.sub.2 HCH.sub.2 CF.sub.2 Cl                                                               9.15   0.83                                           HCFC-252dc CH.sub.3 CClHCF.sub.2 Cl                                                                     15.3   0.49                                           HCFC-252ec CH.sub.3 CFHCCl.sub.2 F                                                                      8.6    0.88                                           HCFC-253ba CFH.sub.2 CFClCFH.sub.2                                                                      17.7   0.43                                           HCFC-253bb CH.sub.3 CFClCF.sub.2 H                                                                      13.8   0.55                                           HCFC-253ea CF.sub.2 HCFHCClH.sub.2                                                                      14.5   0.52                                           HCFC-253eb CClFHCFHCFH.sub.2                                                                            16.5   0.46                                           HCFC-253ec CH.sub.3 CFHCF.sub.2 Cl                                                                      8.0    0.95                                           HCFC-253fa CF.sub.2 HCH.sub.2 CFClH                                                                     14.5   0.52                                           HCFC-253fc CFH.sub.2 CH.sub.2 CF.sub.2 CI                                                               11.5   0.66                                           HCFC-262fa CF.sub.2 HCH.sub.2 CClH.sub.2                                                                14.99  0.50                                           HCFC-262fb CFH.sub.2 CH.sub.2 CFClH                                                                     17.8   0.43                                           HCFC-271b  CH.sub.3 CFClCH.sub.3                                                                        9.95   0.76                                           HCFC-271d  CH.sub.3 CClHCFH.sub.2                                                                       19.44  0.39                                           HCFC-271fb CH.sub.3 CH.sub.2 CFClH                                                                      9.98   0.76                                           ______________________________________                                    

This present class with its OH rate constants between about 8 to about 25 cm³ /molecule/sec×10⁻¹⁴ was unexpected. I discovered this when I compared isomers having the same --CAB-- group wherein --CAB-- is --CCl₂ --, --CH2--, --CClH--, --CClF--, and --CHF-- as the covered compound. I found that the isomers had OH rate constants less than 8 or greater than 25 cm³ /molecule/sec×10⁻¹⁴. For example, CFClHCFHCFClH and CF₂ ClCFHCClH₂ of the present invention have KOH values of 19.1 and 8.4 cm³ /molecule/sec×10⁻¹⁴ respectively as shown in Table II. In contrast, the isomers, CF₂ HCFHCCl₂ H and CCl₂ FCFHCFH₂, have KOH values of 31.3 and 30.0 cm³ /molecule/sec×10⁻¹⁴ respectively as shown in Table VII, and thus, are VOCs.

Also, CFH₂ CFClCF₂ H of the present invention has a KOH of 12.0 cm³ /molecule/sec×10⁻¹⁴ as shown in Table II. In contrast, the isomer, CF₃ CFClCH₃, has a KOH of 1.8 cm³ /molecule/sec×10⁻¹⁴ as shown in Table VII, and thus, has a long atmospheric lifetime. The isomers, CFH₂ CCl₂ CFH₂ and CH₃ CCl₂ CF₂ H, have KOH values of 49.33 and 34.14 cm³ /molecule/sec×10⁻¹⁴ respectively as shown in Table VII and thus, are VOCs.

Additionally, CH₃ CFHCCl₂ F of the present invention has a KOH of 8.6 cm³ /molecule/sec×10⁻¹⁴ as shown in Table II. In contrast, the isomers, CClH₂ CFHCClFH and CFH₂ CFHCCl₂ H, have KOH values of 31.8 and 39.57 cm³ /molecule/sec×10⁻¹⁴ respectively as shown in Table VII, and thus, are VOCs.

Additionally, CF₂ HCH₂ CClH₂ and CFH₂ CH₂ CFClH of the present invention have KOH values of 14.99 and 17.8 cm³ /molecule/sec×10⁻¹⁴ respectively as shown in Table II. In contrast, the isomer, CF₂ ClCH₂ CH₃, has a KOH of 2.9 cm³ /molecule/sec×10⁻¹⁴ as shown in Table VII, and thus, has a long atmospheric lifetime. Additionally, CH₃ CH₂ CFClH of the present invention has a KOH of 9.98 cm³ /molecule/sec×10⁻¹⁴ as shown in Table II. In contrast, the isomer, CFH₂ CH₂ CClH₂, has a KOH value of 35.8 cm³ /molecule/sec×10⁻¹⁴ as shown in Table VII, and thus, is a VOC.

Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention.

For example, Haszeldine, Nature 165, 152 (1950) teaches the reaction of trifluoroiodomethane and acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. By using 3,3,3-trifluoropropyne as a starting material, CF₃ CFClCClH₂ (HCFC-234bb) may be prepared as follows. Commercially available trifluoromethyl iodide may be reacted with acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trifluoropropyne. The 3,3,3-trifluoropropyne may then be reacted with commercially available hydrogen fluoride to form 2,3,3,3-tetrafluoro-1-propene which is then chlorinated to form 1,2-dichloro-2,3,3,3-tetrafluoropropane.

CF₂ ClCFHCClH₂ (HCFC-243ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be dehydrohalogenated to form 1,3-dichloro-1- propyne. The 1,3-dichloro-1-propyne may then be fluorinated to form 1,3-dichloro-1,2-difluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-1,1,2-trifluoropropane.

CFH₂ CFClCF₂ H (HCFC-244ba) may be prepared as follows. Commercially available 1,3-difluoro-2-propanol may be dehydrated to form 1,3-difluoro-1-propene which may then be dehydrohalogenated to form 3-fluoro-1-propyne. The 3-fluoro-1-propyne may then be fluorinated, chlorinated, and fluorinated to form 1,1,2,3-tetrafluoro-2-chloropropane.

CFH₂ CFHCF₂ Cl (HCFC-244ec) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1-dichloro-3-fluoro-1-propene which may then be dehydrohalogenated to form 1-chloro-3-fluoro-1-propyne. The 1-chloro-3-fluoro-1-propyne may then be fluorinated to form 1-chloro-1,2,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3-tetrafluoropropane.

CFClHCH₂ CF₃ (HCFC-244fa) may be prepared as follows. Commercially available 1,1,3-trichloropropene may be fluorinated to form 1,1,1,2,3-pentafluoropropane. The 1,1,1,2,3-pentafluoropropane may then be dehydrohalogenated to form 1,3,3,3-tetrafluoro-1-propene which may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3,3-tetrafluoropropane.

CF₂ HCH₂ CF₂ Cl (HCFC-244fb) may be prepared as follows. Commercially available 2,2,3,3-tetrafluoro-1-propanol may be fluorinated to form 1,1,1,2,2,3-hexafluoropropane which may then be dehydrohalogenated to form 1,3,3-trifluoro-1-propyne. The 1,3,3-trifluoro-1-propyne may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,3,3-tetrafluoropropane.

CH₃ CFClCF₂ H (HCFC-253bb) may be prepared as follows. Commercially available 1,2-dibromopropane may be dehydrohalogenated to form propyne. The propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1,1,2-trifluoropropane.

CH₃ CFHCF₂ Cl (HCFC-253ec) may be prepared as follows. Commercially available 1,2-dichloropropane may be dehydrohalogenated to form 1-chloro-1-propene which may then be dehydrogenated to form 1-chloro-1-propyne. The 1-chloro-1-propyne may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1-fluoro-1-propene which may then be fluorinated to form 1-chloro-1,1,2-trifluoropropane.

The preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF₂ ClCFHCClH₂, CH₃ CFClCF₂ H, and CH₃ CFHCF₂ Cl.

The straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention are listed in Table III below. The unit on the calculated KOH is cm³ /molecule/sec×10⁻¹⁴ and the unit on the calculated lifetime is years in Table III below.

                  TABLE III                                                        ______________________________________                                         Number     Chemical Formula                                                                             KOH    Lifetime                                       ______________________________________                                         HCFC-3541cd                                                                               CH.sub.3 CClHCF.sub.2 CF.sub.2 Cl                                                            12.8   0.59                                           HCFC-354mbd                                                                               CH.sub.3 CClHCFClCF.sub.3                                                                    11.9   0.63                                           HCFC-3551cf                                                                               CFH.sub.2 CH.sub.2 CF.sub.2 CF.sub.2 Cl                                                      12.0   0.63                                           HCFC-3551ec                                                                               CH.sub.3 CF.sub.2 CFHCF.sub.2 Cl                                                             12.8   0.59                                           HCFC-3551ef                                                                               CF.sub.2 HCH.sub.2 CFHCF.sub.2 Cl                                                            15.6   0.48                                           HCFC-3551ff                                                                               CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.2 Cl                                                       10.4   0.73                                           HCFC-355mbf                                                                               CFH.sub.2 CH.sub.2 CFClCF.sub.3                                                              11.5   0.66                                           HCFC-355mcf                                                                               CF.sub.3 CF.sub.2 CH.sub.2 CClH.sub.2                                                        8.93   0.85                                           HCFC-355mdc                                                                               CH.sub.3 CF.sub.2 CClHCF.sub.3                                                               12.0   0.63                                           HCFC-355mdf                                                                               CF.sub.2 HCH.sub.2 CClHCF.sub.3                                                              14.3   0.53                                           HCFC-355meb                                                                               CH.sub.3 CFClCFHCF.sub.3                                                                     11.8   0.64                                           HCFC-355med                                                                               CFH.sub.2 CClHCFHCF.sub.3                                                                    14.1   0.54                                           HCFC-355mfb                                                                               CFH.sub.2 CFClCH.sub.2 CF.sub.3                                                              15.9   0.48                                           HCFC-355mfc                                                                               CF.sub.3 CH.sub.2 CF.sub.2 CClH.sub.2                                                        13.2   0.57                                           HCFC-355mfd                                                                               CF.sub.2 HCCIHCH.sub.2 CF.sub.3                                                              14.9   0.51                                           HCFC-355mfe                                                                               CFClHCFHCH.sub.2 CF.sub.3                                                                    15.1   0.50                                           HCFC-355pcb                                                                               CH.sub.3 CFClCF.sub.2 CF.sub.2 H                                                             15.7   0.48                                           HCFC-355rcc                                                                               CH.sub.3 CF.sub.2 CF.sub.2 CFClH                                                             15.2   0.50                                           HCFC-3631bfs                                                                              CH.sub.3 CH.sub.2 CClFCF.sub.2 Cl                                                            13.4   0.56                                           HCFC-364med                                                                               CH.sub.3 CClHCFHCF.sub.3                                                                     15.0   0.50                                           HCFC-364mff                                                                               CFClHCH.sub.2 CH.sub.2 CF.sub.3                                                              15.5   0.49                                           HCFC-3731ef                                                                               CH.sub.3 CH.sub.2 CFHCF.sub.2 Cl                                                             9.11   0.83                                           HCFC-373mfd                                                                               CH.sub.3 CClHCH.sub.2 CF.sub.3                                                               14.3   0.53                                           HCFC-373mff                                                                               CF.sub.3 CH.sub.2 CH.sub.2 CClH.sub.2                                                        13.2   0.57                                           HCFC-391rff                                                                               CH.sub.3 CH.sub.2 CH.sub.2 CFClH                                                             10.3   0.73                                           HCFC-391sbf                                                                               CH.sub.3 CH.sub.2 CFClCH.sub.3                                                               14.2   0.53                                           ______________________________________                                    

Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention.

For example, R. N. Haszeldine et al., "Addition of Free Radicals to Unsaturated Systems. Part XIII. Direction of Radical Addition to Chloro-1:1-difluoroethylene", J. of Amer. Chem. Soc., 2193 (1957) teach the reaction of trifluoroiodomethane with chloro-1:1-difluoroethylene to prepare 3-chloro-1:1:1:2:2-pentafluoro-3-iodopropane which is then chlorinated to form 1,1-dichloro-2,2,3,3,3-pentafluoropropane (known in the art as HCFC-225ca). This known method can be modified to form CF₃ CF₂ CH₂ CClH₂ (HCFC-355mcf) as follows. Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1,1,2,2-pentafluoro-4-iodobutane which is then chlorinated to form 1,1,1,2,2-pentafluoro-4-chlorobutane.

CH₃ CF₂ CFHCF₂ Cl (HCFC-3551ec) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may then be dehydrohalogenated to form 1-chloro-3,3-difluoro-1-butene. The 1-chloro-3,3-difluoro-1-butene may then be dehydrogenated to form 1-chloro-3,3-difluoro-1-propyne which may then be fluorinated to form 1-chloro-1,2,3,3-tetrafluoro-1-butene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3,3-pentafluorobutane.

CF₃ CH₂ CH₂ CF₂ Cl (HCFC-3551ff) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butyne. The hexafluoro-2-butyne may be hydrogenated to form 1,1,1,4,4,4-hexafluorobutane which may be chlorinated to form 1-chloro-1,1,4,4,4-pentafluorobutane.

CFH₂ CH₂ CFClCF₃ (HCFC-355mbf) may be prepared as follows. Commercially available 1,4-dichloro-2-butyne may be reacted with commercially available hydrogen fluoride to form 1,4-dichloro-2-fluoro-2-butene which may be fluorinated to form 1,2,4-trifluoro-2-butene. The 1,2,4-trifluoro-2-butene may be reacted with commercially available hydrogen chloride to form 2-chloro-1,2,4-trifluorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, and fluorinated to form 2-chloro-1,1,1,2,4-pentafluorobutane.

CH₃ CF₂ CClHCF₃ (HCFC-355mdc) may be prepared as follows. Commercially available 3,4-dichloro-1-butene may be dehydrogenated to form 3,4-dichloro-1-butyne which may be reacted with commercially available hydrogen fluoride to form 1,2-dichloro-3,3-difluorobutane. The 1,2-dichloro-3,3-difluorobutane may be dehydrogenated to form 1,2-dichloro-3,3-difluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,3,3-tetrafluorobutane. The 2-chloro-1,1,3,3-tetrafluorobutane may be dehydrogenated to form 2-chloro-1,1,3,3-tetrafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,1,3,3-pentafluorobutane.

CH₃ CFClCFHCF₃ (HCFC-355meb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-1-butene. The 3-chloro-1,3-difluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4-tetrafluorobutane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-1-butene. The 3-chloro-1,1,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4,4-pentafluorobutane.

CH₃ CFClCF₂ CF₂ H (HCFC-355pcb) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrogenated to form 3-chloro-1,2,3-trifluoro-1-butene. The 3-chloro-1,2,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,3,4,4-pentafluorobutane.

CH₃ CF₂ CF₂ CFClH (HCFC-355rcc) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may be dehydrogenated to form 1-chloro-2,3,3-trifluoro-1-butene. The 1-chloro-2,3,3-trifluoro-1-butene may be fluorinated to form 1-chloro-1,2,2,3,3-pentafluorobutane.

CH₃ CClHCFHCF₃ (HCFC-364med) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available hydrogen fluoride to form 1,3-dichloro-2-fluorobutane which may be dehydrohalogenated to form 1,3-dichloro-1-butene. The 1,3-dichloro-l-butene may be fluorinated to form 2-chloro-3,4,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1,1-difluoro-1-butene. The 3-chloro-1,1-difluoro-1-butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafluorobutane.

The preferred straight chain hydrochlorofluorocarbons having 4 carbon atoms are CH₃ CF₂ CFHCF₂ Cl, CF₃ CH₂ CH₂ CF₂ Cl, CFH₂ CH₂ CFClCF₃, CH₃ CF₂ CClHCF₃, CH₃ CFClCFHCF₃, CH₃ CFClCF₂ CF₂ H, CH₃ CF₂ CF₂ CFClH, and CH₃ CClHCFHCF₃.

The branched chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention are listed in Table IV below. The unit on the calculated KOH is cm³ /molecule/sec×10⁻¹⁴ and the unit on the calculated lifetime is years in Table IV below.

                  TABLE IV                                                         ______________________________________                                         Number     Chemical Formula                                                                             KOH    Lifetime                                       ______________________________________                                         HCFC-345kms                                                                               CH.sub.3 C(CF.sub.3)FCFCl.sub.2                                                              9.11   0.83                                           HCFC-34511s                                                                               CH.sub.3 C(CF.sub.2 Cl)FCF.sub.2 Cl                                                          9.11   0.83                                           HCFC-3551ms                                                                               CH.sub.3 C(CF.sub.3)HCF.sub.2 Cl                                                             8.3    0.91                                           HCFC-355mop                                                                               CF.sub.2 HC(CClH.sub.2)HCF.sub.3                                                             14.5   0.52                                           HCFC-355mps                                                                               CH.sub.3 C(CF.sub.2 H)ClCF.sub.3                                                             15.3   0.50                                           HCFC-355mrs                                                                               CH.sub.3 C(CFClH)FCF.sub.3                                                                   15.1   0.50                                           HCFC-373mss                                                                               CH.sub.3 C(CH.sub.3)ClCF.sub.3                                                               13.4   0.56                                           ______________________________________                                    

Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.

CH₃ C(CF₃)HCF₂ Cl (HCFC-3551ms) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 1-chloro-1-fluoro-2-methylpropene. The 1-chloro-1-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3,3-difluoro-2-methylpropene. The 3-chloro-3,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrogenated to form 3-chloro-1,3,3-trifluoro-2-methylpropene. The 3-chloro-1,3,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene. The 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,3,3,3-pentafluoro-2-methylpropane.

CH₃ C(CF₂ H)ClCF₃ (HCFC-355mps) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1,1,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3,3-difluoro-2-methylpropene. The 3,3-difluoro-2-methytpropene may be fluorinated to form 1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 1,3,3-trifluoro-2-methylpropene. The 1,3,3-trifluoro-2-methylpropene may be fluorinated to form 1,1,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-methylpropene. The 1,1,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1,2-dichloro-1,1,4,4-tetrafluoro-2-methylpropane which may be fluorinated to form 2-chloro-1,1,1,3,3-pentafluoro-2-methylpropane.

CH₃ C(CFClH)FCF₃ (HCFC-355mrs) may be prepared as follows. Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3-fluoro-2-methylpropene. The 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,3-difluoro-2-methylpropene. The 3-chloro-1,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1,1,3-trifluoro-2-methylpropene. The 3-chloro-1,1,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1,2,3,3,3-pentafluoro-2-methylpropane.

The preferred branched hydrochlorofluorocarbons having 4 carbon atoms are CH₃ C(CF₃)HCF₂ Cl, CH₃ C(CF₂ H)ClCF₃, and CH₃ C(CFClH)FCF₃.

The branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention are listed in Table V below. The unit on the calculated KOH is cm³ /molecule/sec×10⁻¹⁴ and the unit on the calculated lifetime is years in Table V below.

                  TABLE V                                                          ______________________________________                                         Number     Chemical Formula                                                                               KOH    Lifetime                                     ______________________________________                                         HCFC-356mlfq                                                                              CFH.sub.2 CH.sub.2 C(CF.sub.2 Cl)FCF.sub.3                                                     12.0   0.63                                         HCFC-3571csp                                                                              CF.sub.2 ClCF.sub.2 C(CH.sub.3)FCF.sub.2 H                                                     15.1   0.50                                         HCFC-3571sem                                                                              CF.sub.3 CFHC(CH.sub.3)FCF.sub.2 Cl                                                            14.6   0.52                                         HCFC-357mbsp                                                                              CF.sub.3 CFClC(CH.sub.3)FCF.sub.2 H                                                            15.0   0.50                                         HCFC-357mcpo                                                                              CF.sub.3 CF.sub.2 C(CF.sub.2 H)HCClH.sub.2                                                     14.7   0.51                                         HCFC-357mcsp                                                                              CF.sub.3 CF.sub.2 C(CH.sub.3)ClCF.sub.2 H                                                      13.7   0.55                                         HCFC-357mcsr                                                                              CF.sub.3 CF.sub.2 C(CH.sub.3)FCFClH                                                            15.1   0.50                                         HCFC-357mlcs                                                                              CH.sub.3 CF.sub.2 C(CF.sub.2 Cl)HCF.sub.3                                                      10.7   0.71                                         HCFC-357mmbs                                                                              CH.sub.3 CFClC(CF.sub.3)HCF.sub.3                                                              9.5    0.80                                         HCFC-357mmel                                                                              CF.sub.2 ClCHFC(CH.sub.3)FCF.sub.3                                                             14.3   0.53                                         HCFC-357mmfo                                                                              CH.sub.2 ClCH.sub.2 C(CF.sub.3)FCF.sub.3                                                       8.8    0.86                                         HCFC-357mmfq                                                                              CFH.sub.2 CH.sub.2 C(CF.sub.3)ClCF.sub.3                                                       11.5   0.66                                         HCFC-357mmfr                                                                              CFClHCH.sub.2 C(CF.sub.3)HCF.sub.3                                                             14.0   0.54                                         HCFC-357mofm                                                                              CF.sub.3 CH.sub.2 C(CClH.sub.2)FCF.sub.3                                                       14.1   0.54                                         HCFC-357msem                                                                              CF.sub.3 CFHC(CH.sub.3)ClCF.sub.3                                                              13.0   0.57                                         HCFC-358mcsr                                                                              CF.sub.3 CF.sub.2 C(CH.sub.3)FCClFH                                                            13.8   0.55                                         HCFC-366mmds                                                                              CH.sub.3 6ClHC(CF.sub.3)HCF.sub.3                                                              12.8   0.59                                         HCFC-366mmfo                                                                              CClH.sub.2 CH.sub.2 C(CF.sub.3)HCF.sub.3                                                       13.2   0.57                                         HCFC-37S1css                                                                              CF.sub.2 ClCF.sub.2 C(CH.sub.3)FCH.sub.3                                                       10.7   0.71                                         HCFC-375mbss                                                                              CF.sub.3 CF? 1C(CH.sub.3)FCH.sub.3                                                             10.7   0.71                                         HCFC-3931ess                                                                              CF.sub.2 ClCFHC(CH.sub.3)HCH.sub.3                                                             12.1   0.62                                         HCFC-393mdss                                                                              CF.sub.3 CClHC(CH.sub.3)HCH.sub.3                                                              10.0   0.76                                         HCFC-393sfms                                                                              CH.sub.3 CH.sub.2 C(CF.sub.3)ClCH.sub.3                                                        13.0   0.58                                         HCFC-3-11-1rfss                                                                           CFClHCH.sub.2 C(CH.sub.3)HCH.sub.3                                                             13.4   0.56                                         ______________________________________                                    

Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention.

CFH2CH2C(CF2C1)FCF3 (HCFC-356mlfq) may be prepared as follows. Commercially available 1,4-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,4-dichloro-2-trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form 1,4-dichloro-3-trifluoromethyl-1-butene. The 1,4-dichloro-3-trifluoromethyl-1-butene may be hydrogenated to form 1,4-dichloro-2-trifluoromethylbutane which may be fluorinated to form 1-chloro-2-trifluoromethyl-4-fluorobutane. The 1-chloro-2-trifluoromethyl-4-fluorobutane may be dehydrogenated to form 1-chloro-2-trifluoromethyl-4-fluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane. The 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane may be dehydrohalogenated to form 1-chloro-2-trifluoromethyl-1,4-difluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,1,2,4-tetrafluorobutane.

CF₃ CFHC(CH₃)FCF₂ Cl (HCFC-3571sem) may be prepared as follows. Commercially available 1,4-dichloro-2-butene may be reacted with commercially available iodomethane to form 1,4-dichloro-3-iodo-2-methylbutane which may be dehydrohalogenated to form 1,4-dichloro-3-methyl-1-butene. The 1,4-dichloro-3-methyl-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4-trifluorobutane which may be dehydrohalogenated to form 1,1-difluoro-3-methyl-4-chloro-1-butene. The 1,1-difluoro-3-methyl-4-chloro-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,4,4-tetrafluorobutane which may be dehydrogenated to form 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1-butene. The 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,2,3,4,4,4-hexafluorobutane which may be dehydrohaloganated to form 1-chloro-2-methyl-1,3,4,4,4-pentafluoro-1-butene. The 1-chloro-2-methyl-1,3,4,4,4-pentafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.

CF₃ CFClC(CH₃)FCF₂ H (HCFC-357mbsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-2-methyl-1,1,1, 4,4,4-hexafluoropropane which may be fluorinated to form 2-methyl-3-chloro-1,1,1,2,3,4,4-heptafluorobutane. The 2-methyl-3-chloro-1,1,1,2,3,4,4-heptafluorobutane may be dehalogenated to form 3-chloro-2-methyl-1,1,3,4,4,4-hexafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-methyl-1,1,2,3,4,4,4-heptafluorobutane.

CF₃ CF₂ C(CH₃)ClCF₂ H (HCFC-357mcsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with iodomethane to form 2-methyl-2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-methyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 2-methyl-1,1,3,3,4,4,4-heptafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-2-methyl-1,1,3,3,4,4,4-heptafluorobutane.

CH₃ CF₂ C(CF₂ Cl)HCF₃ (HCFC-357mlcs) may be prepared as follows. Commercially available 1,3-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,3-dichloro-2-trifluoromethyl-3-iodobutane which may be fluorinated to form 1,3,3-trifluoro-2-trifluoromethylbutane. The 1,3,3-trifluoro-2-trifluoromethylbutane may be dehydrogenated to form 1,3,3-trifluoro-2-trifluoromethyl-1-butene which may be fluorinated to form 1,1,2,3,3-pentafluoro-2-trifluoromethylbutane. The 1,1,2,3,3-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-trifluoromethyl-1-butene which may be reacted with commercially available hydrogen chloride to form 1-chloro-1,1,3,3-tetrafluoro-2-trifluoromethylbutane.

CH₃ CFClC(CF₃)HCF₃ (HCFC-357mmbs) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane which may be fluorinated to form 2-trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,3,4,4,4-nonafluorobutane may be dehalogenated to form 3-trifluoromethyl-1,1,2,3,4,4,4-heptafluoro-1-butene which may be hydrogenated to form 2-trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,4,4-heptafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluoro-1-butene which may be hydrogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluorobutane. The 3-trifluoromethyl-1,2,3,4,4,4-hexafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-2,3,4,4,4-pentafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2-trifluoromethyl-1,1,1,2,3-pentafluorobutane. The 3-chloro-2-trifluoromethyl-1,1,1,1,2,3-pentafluorobutane may be dehalogenated to form 3-chloro-2-trifluoromethyl-1,1,3-trifluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-trifluoromethyl-1,1,1,3-tetrafluorobutane.

CF₂ ClCHFC(CH₃)FCF₃ (HCFC-357mmel) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methylperfluorobutane. The 2-methylperfluorobutane may be dehalogenated to form 1,1,2,3,4,4,4-heptafluoro-3-methyl-1-butene which may be reacted with commercially available hydrogen chloride to form 4-chloro-1,1,1,2,3,4,4-heptafluoro-2-methylbutane.

The method of R. N. Haszeldine et al., supra, can be modified to form CH₂ ClCH₂ C(CF₃)FCF₃ (HCFC-357 mmfo) as follows. Commercially available perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trifluoromethyl-1,1,1,2-tetrafluoro-4-iodobutane which may then be chlorinated to form 2-trifluoromethyl-1,1,1,2-tetrafluoro-4-chlorobutane.

CFH₂ CH₂ C(CF₃)ClCF₃ (HCFC-357mmfq) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be fluorinated to form 2-chloro-2-trifluoromethyl-perfluorobutane. The 2-chloro-2-trifluoromethyl-perfluorobutane may be dehalogenated to form 3-chloro-3-trifluoromethyl-1,1,2,4,4,4-hexafluoro-1-butene which may be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,3,4,4-hexafluorobutane. The 2-chloro-2-trifluoromethyl-1,1,1,3,4,4-hexafluorobutane may be fluorinated to form 3-chloro-3-trifluoromethyl-1,4,4,4-tetrafluoro-1-butene which may then be hydrogenated to form 2-chloro-2-trifluoromethyl-1,1,1,4-tetrafluorobutane.

CF₃ CFHC(CH₃)ClCF₃ (HCFC-357msem) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be chlorinated to form 2,3,3-trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane. The 2,3,3-trichloro-1,1,1,4,4,4-hexafluoro-2-methylbutane may be dehalogenated to form 3-chloro-1,1,1,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane. The 3-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane may be dehydrohalogenated to form 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-methylbutane.

CF₃ CF₂ C(CH₃)FCClFH (HCFC-358mcsr) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methyl-perfluorobutane. The 2-methyl-perfluorobutane may be dehalogenated to form 2-methyl-perfluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 1,1,2,3,3,4,4,4-octafluoro-2-methylbutane. The 1,1,2,3,3,4,4,4-octafluoro-2-methylbutane may be dehalogenated to form 1,3,3,4,4,4-hexafluoro-2-methyl-1-butene which may be chlorinated to form 1,2-dichloro-1,3,3,4,4,4-hexafluoro-2-methylbutane. The 1,2-dichloro-1,3,3,4,4,4-hexafluoro-2-methylbutane may be dehydrohalogenated to form 1-chloro-1,3,3,4,4,4-hexafluoro-2-methyl-1-butene which may be reacted with commercially available hydrogen fluoride to form 1-chloro-1,2,3,3,4,4,4-heptafluoro-2-methylbutane.

CH₃ CClHC(CF₃)HCF₃ (HCFC-366mmds) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-1,1,1,4,4,4-hexafluoro-2-methyl-2-butene. The 3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethyl-2-butene may be hydrogenated to form 3-iodo-1,1,1,4,4,4-hexafluoro-2-trifluoromethylbutane which may be dehydrohalogenated to form 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl-1-butene. The 2-iodo-1,1,4,4,4-pentafluoro-3-trifluoromethyl-1-butene may be hydrogenated to form 3-iodo-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-chloro-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4,4-pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-1,4,4,4-tetrafluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1,4-tetrafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4-tetrafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-4,4,4-trifluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1,1-trifluoro-2-trifluoromethylbutane.

The preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH₂ CH₂ C(CF₂ Cl)FCF₃, CF₃ CFHC(CH₃)FCF₂ Cl, CF₃ CFC₁ C(CH₃)FCF₂ H, CF₃ CF₂ C(CH₃)ClCF₂ H, CH₃ CF₂ C(CF₂ Cl)HCF₃, CH₃ CFClC(CF₃) HCF₃, CF₂ ClCHFC(CH₃)FCF₃, CH₂ ClCH₂ C(CF₃) FCF₃, CFH₂ CH₂ C (CF₃) ClCF₃, CF₃ CFHC(CH₃)ClCF₃, CF₃ CF₂ C(CH₃) FCClFH, and CH₃ CClHC(CF₃) HCF₃.

Other advantages of the invention will become apparent from the following description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Known solvents may be blended with the hydrochlorofluorocarbons of the present invention. Examples of useful known solvents are listed in Table VI below.

                  TABLE VI                                                         ______________________________________                                         Number             Chemical Formula                                            ______________________________________                                         HCFC-234cc         CF.sub.2 ClCF.sub.2 CClH.sub.2                              HCFC-234cd         CH.sub.2 FCF.sub.2 CFCl.sub.2                               HCFC-244ca         CF.sub.2 HCF.sub.2 CClH.sub.2                               HCFC-244cb         CFH.sub.2 CF.sub.2 CFClH                                    HCFC-253ca         CFH.sub.2 CF.sub.2 CCIH.sub.2                               HCFC-253cb         CH.sub.3 CF.sub.2 CFClH                                     ______________________________________                                    

HCFC-234cc may be formed by any known method such as the reaction of 1,1,1,2,2,3-hexachloropropane with antimony pentachloride and hydrogen fluoride at 100° C. HCFC-234cd may be formed by any known method such as the reaction of 1,1,1-trichloro-2,2,3-trifluoropropane with antimony pentachloride and hydrogen fluoride at 120° C.

HCFC-244ca may be formed by any known method such as the reaction of 1,1,2,2,3-pentachloropropane with antimony pentachloride and hydrogen fluoride at 100° C. HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1,1,2,2-tetrafluoropropane with cesium fluoride and tetrabutylammonium bromide at 150° C.

HCFC-253ca may be formed by any known method such as the reaction of 1,2,3-trichloro-2-fluoropropane with niobium pentachloride and hydrogen fluoride at 100° C. HCFC-253cb may be formed by any known method such as the reaction of 1,1,2,2-tetrachloropropane with tantalum pentafluoride and hydrogen fluoride at 130° C.

The present hydrochlorofluorocarbons may be used as solvents in vapor degreasing, solvent cleaning, cold cleaning, dewatering, dry cleaning, defluxing, decontamination, spot cleaning, aerosol propelled rework, extraction, particle removal, and surfactant cleaning applications. In these uses, the object to be cleaned is immersed in one or more stages in the liquid and/or vaporized solvent or is sprayed with the liquid solvent. Elevated temperatures, ultrasonic energy, and/or agitation may be used to intensify the cleaning effect.

The present hydrochlorofluorocarbons are also useful as blowing agents, Rankine cycle and absorption refrigerants, and power fluids and especially as refrigerants for centrifugal refrigeration chillers.

The present invention is more fully illustrated by the following non-limiting Examples.

COMPARATIVES

The hydrochlorofluorocarbons having 3 carbon atoms and 1 or 2 chlorine atoms in Table VII below are isomers of the compounds of the present invention. As discussed above, these compounds have OH rate constants which are less than 8 cm³ /molecule/sec×10⁻¹⁴ or greater than 25 cm³ /molecule/sec×10⁻¹⁴. The unit on the KOH is cm³ /molecule/sec×10⁻¹⁴ and the unit on the lifetime is years in Table VII below.

                  TABLE VII                                                        ______________________________________                                         Number     Chemical Formula                                                                               KOH    Lifetime                                     ______________________________________                                         HCFC-243eb CF.sub.2 HCFHCCl.sub.2 H                                                                       31.3   0.24                                         HCFC-243ed CCl.sub.2 FCFHCFH.sub.2                                                                        30.0   0.25                                         HCFC-244bb CF.sub.3 CFClCH.sub.3                                                                          1.8    4.20                                         HCFC-252aa CFH.sub.2 CCl.sub.2 CFH.sub.2                                                                  49.33  0.15                                         HCFC-252ab CH.sub.3 CCl.sub.2 CF.sub.2 H                                                                  34.14  0.22                                         HCFC-252ea CClH.sub.2 CFHCClFH                                                                            31.8   0.24                                         HCFC-252eb CFH.sub.2 CFHCCl.sub.2 H                                                                       39.57  0.19                                         HCFC-262fc CF.sub.2 ClCH.sub.2 CH.sub.3                                                                   2.9    2.61                                         HCFC-271fa CFH.sub.2 CH.sub.2 CClH.sub.2                                                                  35.8   0.21                                         ______________________________________                                    

Examples 1-85

Each solvent listed in Tables II through V is added to mineral oil in a weight ratio of 50:50 at 27° C. Each solvent is miscible in the mineral oil.

Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims. 

What is claimed is:
 1. A hydrochlorofluorocarbon having 3 to 5 carbon atoms, 1 to 2 chlorine atoms, and OH rate constants between about 8 and about 25 cm³ /molecule/sec×10⁻¹⁴ wherein said hydrochlorofluorocarbon is selected from the group consisting of CFH₂ CCl₂ CF₃, CFH₂ CFClCF₂ Cl, CF₂ ClCFHCClH₂, CH₃ CFHCCl₂ F, CFH₂ CFClCFH₂, CH₃ CFClCF₂ H, CF₂ HCFHCClH₂, CClFHCFHCFH₂, CH₃ CFHCF₂ Cl, CF₂ HCH₂ CFClH, CFH₂ CH₂ CF₂ Cl, CF₂ HCH₂ CClH₂, CFH₂ CH₂ CFClH, CH₃ CClHCFH₂, CH₃ CH₂ CFClH, CH₃ CH₂ CClFCF₂ Cl, CH₃ CClHCF₂ CF₂ Cl, CH₃ CClHCFClCF₃, CFH₂ CH₂ CF₂ CF₂ Cl, CH₃ CF₂ CFHCF₂ Cl, CF₂ HCH₂ CFHCF₂ Cl, CF₃ CH₂ CH₂ CF₂ Cl, CFH₂ CH₂ CFClCF₃, CF₃ CF₂ CH₂ CClH₂, CH₃ CF₂ CClHCF₃, CF₂ HCH₂ CClHCF₃, CH₃ CFClCFHCF₃, CFH₂ CClHCFHCF₃, CFH₂ CFClCH₂ CF₃, CF₃ CH₂ CF₂ CClH₂, CF₂ HCClHCH₂ CF₃, CFClHCFHCH₂ CF₃, CH₃ CFClCF₂ CF₂ H, CH₃ CF₂ CF₂ CFClH, CH₃ CClHCFHCF₃, CFClHCH₂ CH₂ CF₃, CH₃ CH₂ CFHCF₂ Cl, CF₃ CH₂ CH₂ CClH₂, CH₃ CH₂ CH₂ CFClH, CH₃ C(CF₃)FCFCl₂, CH₃ C(CF₂ Cl)FCF₂ Cl, CH₃ C(CF₃)HCF₂ Cl, CF₂ HC(CClH₂)HCF₃, CH₃ C(CF₂ H)ClCF₃, CH₃ C(CFClH)FCF₃, CH₃ C(CH₃)ClCF₃, CFH₂ CH₂ C(CF₂ Cl) FCF₃, CF₂ ClCF₂ C(CH₃)FCF₂ H, CF₃ CFHC(CH₃)FCF₂ Cl, CF₃ CFClC(CH₃)FCF₂ H, CF₃ CF₂ C(CF₂ H)HCClH₂, CF₃ CF₂ C(CH₃)ClCF₂ H, CF₃ CF₂ C(CH₃)FCFClH, CH₃ CF₂ C(CF₂ Cl)HCF₃, CF₂ ClCHFC(CH₃)FCF₃, CFH₂ CH₂ C(CF₃)ClCF₃, CFClHCH₂ C(CF₃)HCF₃, CF₃ CH₂ C(CClH₂)FCF₃, CF₃ CFHC(CH₃)ClCF₃, CF₃ CF₂ C(CH₃)FCClFH, CH₃ CClHC (CF₃)HCF₃, CClH₂ CH₂ C(CF₃)HCF₃, CF₂ ClCF₂ C(CH₃)FCH₃, CF₃ CFClC(CH₃)FCH₃, CF₂ ClCFHC (CH₃) HCH₃, CF₃ CClHC(CH₃)HCH₃, CH₃ CH₂ C(CF₃)ClCH₃, and CFClHCH₂ C(CH₃)HCH₃.
 2. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbon is selected from the group consisting of CFH₂ CCl₂ CF₃, CFH₂ CFClCF₂ Cl, CF₂ ClCFHCClH₂, CF₃ CClHCFH₂, CH₃ CClHCF₂ Cl, CH₃ CFHCCl₂ F, CFH₂ CFClCFH₂, CH₃ CFClCF₂ H, CF₂ HCFHCClH₂, CClFHCFHCFH₂, CH₃ CFHCF₂ Cl, CF₂ HCH₂ CFClH, CFH₂ CH₂ CF₂ Cl, CF₂ HCH₂ CClH₂, CFH₂ CH₂ CFClH, CH₃ CClHCFH₂, and CH₃ CH₂ CFClH.
 3. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CH₃ CH₂ CClFCF₂ Cl, CH₃ CClHCF₂ CF₂ Cl, CH₃ CClHCFClCF₃, CFH₂ CH₂ CF₂ CF₂ Cl, CH₃ CF₂ CFHCF₂ Cl, CF₂ HCH₂ CFHCF₂ Cl, CF₃ CH₂ CH₂ CF₂ Cl, CFH₂ CH₂ CFClCF₃, CF₃ CF₂ CH₂ CClH₂, CH₃ CF₂ CClHCF₃, CF₂ HCH₂ CClHCF₃, CH₃ CFClCFHCF₃, CFH₂ CClHCFHCF₃, CFH₂ CFClCH₂ CF₃, CF₃ CH₂ CF₂ CClH₂, CF₂ HCClHCH₂ CF₃, CFClHCFHCH₂ CF₃, CH₃ CFClCF₂ CF₂ H, CH₃ CF₂ CF₂ CFClH, CH₃ CClHCFHCF₃, CFClHCH₂ CH₂ CF₃, CH₃ CH₂ CFHCF₂ Cl, CH₃ CClHCH₂ CF₃, CF₃ CH₂ CH₂ CClH₂, CH₃ CH₂ CH₂ CFClH, and CH₃ CH₂ CFClCH₃.
 4. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CH₃ CF₂ CFHCF₂ Cl, CF₃ CH₂ CH₂ CF₂ Cl, CFH₂ CH₂ CFClCF₃, CH₃ CF₂ CClHCF₃, CH₃ CFClCFHCF₃, CH₃ CFClCF₂ CF₂ H, CH₃ CF₂ CF₂ CFClH, and CH₃ CClHCFHCF₃.
 5. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CH₃ C(CF₃)FCFCl₂, CH₃ C(CF₂ Cl)FCF₂ Cl, CH₃ C(CF₃)HCF₂ Cl, CF₂ HC(CClH₂)HCF₃, CH₃ C(CF₂ H)ClCF₃, CH₃ C(CFClH)FCF₃, and CH₃ C(CH₃)ClCF₃.
 6. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CH₃ C(CF₃)HCF₂ Cl, CH₃ C(CF₂ H)ClCF₃, and CH₃ C(CFClH)FCF₃.
 7. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CFH₂ CH₂ C(CF₂ Cl)FCF₃, CF₂ ClCF₂ C(CH₃)FCF₂ H, CF₃ CFHC(CH₃)FCF₂ Cl, CF₃ CFClC(CH₃)FCF₂ H, CF₃ CF₂ C(CF₂ H)HCClH₂, CF₃ CF₂ C(CH₃)ClCF₂ H, CF₃ CF₂ C(CH₃)FCFClH, CH₃ CF₂ C(CF₂ Cl)HCF₃, CF₂ ClCHFC(CH₃)FCF₃, CFH₂ CH₂ C(CF₃)ClCF₃, CFClHCH₂ C(CF₃)HCF₃, CF₃ CH₂ C(CClH₂)FCF₃, CF₃ CFHC(CH₃)ClCF₃, CF₃ CF₂ C (CH₃)FCClFH, CH₃ CClHC(CF₃)HCF₃, CClH₂ CH₂ C(CF₃)HCF₃, CF₂ ClCF₂ C(CH₃)FCH₃, CF₃ CFClC(CH₃)FCH₃, CF₂ ClCFHC(CH₃) HCH₃, CF₃ CClHC(CH₃)HCH₃, CH₃ CH₂ C(CF₃) ClCH₃, and CFClHCH₂ C(CH₃)HCH₃ .
 8. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CFH₂ CH₂ C(CF₂ Cl)FCF₃, CF₃ CFHC(CH₃)FCF₂ Cl, CF₃ CFClC(CH₃)FCF₂ H, CF₃ CF₂ C(CH₃)ClCF₂ H, CH₃ CF₂ C(CF₂ Cl)HCF₃, CF₂ ClCHFC(CH₃)FCF₃, CH₂ ClCH₂ C(CF₃)FCF₃, CFH₂ CH₂ C(CF₃) ClCF₃, CF₃ CFHC(CH₃)ClCF₃, CF₃ CF₂ C(CH₃) FCClFH, and CH₃ CClHC(CF₃)HCF₃ .
 9. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbon is CF₂ ClCFHCClH₂.
 10. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbon is CH₃ CFClCF₂ H. 